Synergistic composition and use thereof

ABSTRACT

Synergistic mixture of (1) the reaction product of from one to two mole proportions of amino compound and one mole proportion of polyhalopolyhydropolycyclicdicarboxylic acid or anhydride and (2) salt of oxyalkylenated alcohol phosphate and amino compound.

United States Patent Latos et al.

[451 Jan. 18,1972

1541 SYNERGISTIC COMPOSITION AND USE THEREOF [72] Inventors: Edwin J. Latos, Chicago; Robert H.

Rosenwald, Western Springs, both of Ill.

[73] Assignee: Universal Oil Products Company, Des

Plaines, Ill.

[52] 11.8. Cl ..252/32.5, 252/8.l, 252/400, 260/45 .8, 424/224 [51] Int. Cl. ..C 10111 1/46 [58] Field of Search ..252/32.5, 32.7 E, 400; 260/458, 45.9, 801, 808, 814; 44/69 P [56] References Cited UNITED STATES PATENTS 2,683,691 7/1954 Thorpeetal. ..252/32.5

2,882,228 4/1959 Watson et al ..252/32.5 3,063,820 1/1962 Chenicek ..252/32.5 3,088,911 5/1963 Staffin et al ..252/34 3,169,923 2/1965 Guarnaccio et al. .252/32.5 3,205,170 9/ 1965 Pollitzer ..252/32.5 3,208,939 9/196 Latos et a1. ..252/5 1 .5 3,238,132 3/1966 Cyba ..252/32.7 3,251,771 5/1966 Benoit 252/32 7 3,336,237 8/1967 Malone et al. 252/32 5 3,362,906 l/1968 Cyba ..44/71 Primary ExaminerDaniel E. Wyman Assistant Examiner-I. Vaughn Attorney-James R. Hoatson, Jr. and Bernard L. Kramer [57] ABSTRACT Synergistic mixture of 1) the reaction product of from one to two mole proportions of amino compound and one mole proportion of polyhalopolyhydropolycyclicdicarboxylic acid or anhydride and (2) salt of oxyalkylenated alcohol phosphate and amino compound.

11 Claims, No Drawings 1 SYN ERGISTIC COMPOSITION AND USE THEREOF CROSS-REFERENCE TO RELATED APPLICATIONS This is a continuation-in-part of application Ser. No. 591,990 filed Nov. 4, 1966 and now abandoned.

BACKGROUND OF THE INVENTION Heretofore, it has been demonstrated by one of the present applicants and others associated with him that the reaction products of polyhalopolyhydropolycyclicdicarboxylic acid or derivatives thereof with certain amino compounds possess desirable properties as additives to organic substrates and particularly in lubricating oils. It also has been demonstrated that phosphate salts of such reaction products also were extremely effective as additives for such use.

DESCRIPTION OF THE INVENTION The present invention is based on the discovery by the present applicants that mixtures of the reaction products and of certain phosphate salts are very effective additives for use in organic substrates and particularly in lubricating oils. These mixtures appear to offer improved properties in special applications.

The mixture produces a synergistic effect as is demonstrated in example IX of the present application, in which a direct comparison is made when using a specified concentration of each component separately and when using the same total amount of additive consisting of a mixture of the two components. As is shown in this example, a higher operating load was obtained before seizure. This increase in load is a surprising discovery and would not normally be expected.

In one embodiment the present invention relates to a synergistic mixture of 1) reaction product of from one to two mole proportions of amino compound and one mold proportion polyhalopolyhydropolycyclicdicarboxylic acid or anhydride and (2) salt of phosphorus compound and amino compound.

in a specific embodiment, the polyhalopolyhydropolycyclicdicarboxylic acid or anhydride is 5,6,7,8,9,9-hexochlorol,2,3,4,4a,5,8,8a-octahydro-5 ,8-methano-2,3- naphthylenedicarboxylic acid or anhydride and the amino compound is a long-chain alkyl monoamine containing from about eight to about 26 carbon atoms or an N-alkyldiaminoalkane containing from about eight to about 26 carbon atoms in said alkyl and from about two to about six carbon atoms in said alkane.

In another embodiment, the present invention relates to the use of the above mixture as an additive in organic substrates and particularly in lubricating oil.

As hereinbefore set forth, a preferred reactant used in preparing the reaction product for use in the mixture of the present invention is 5,6,7,8,9,9-hexachloro-l,2,3,4,4a,5,8,8aoctahydro-5,8-methano-2,3-naphthylenedicarboxylic acid or anhydride, the latter also referred to herein as A anhydride. This acid as well as other acids which may be used, but not necessarily with equivalent results, may be illustrated by the following general formula in which X is selected from the group consisting of halogen and particularly chlorine and/0r bromine, hydrogen and an alkyl radical of from one to and preferably from one to four carbon atoms, at least two of the X's being halogen, Y is selected from the group consisting of halogen, hydrogen and an alkyl radical of one to 10 and preferably from one to four carbon atoms, m is an integer of from I to 4, n ranges from zero to 4 and p ranges from zero to 4.

The above structure illustrates the dicarboxylic acid. In the interest of simplicity, the corresponding anhydride is not illustrated, but is readily ascertainable from the above structure. As hereinbefore set forth, a particularly preferred acidic compound is 5,6,7,8,9,9-hexachloro-l,2,3,4,4a,5,8,8a-octahydro- 5,8-methano-2,3-naphthalenedicarboxylic acid. Other preferred acidic compounds include 5,6,7,8,9,9-hexachlorol,2,3,4,4a,5,8,8a-octahydro-l ,4,5,8-dimethano-2,3- naphthalenedicarboxylic acid, l,4,5,6,7,7-hexachlorodicyclo- (2.2.l)-5-hepene-2,3-dicarboxylic acid, and the corresponding anhydrides.

While the acid or anhydride set forth above is preferred, it is understood that an ester of the acid may be used. Any suitable ester may be used and is prepared by reacting the acid with an alcohol under conditions to liberate water. While the alcohol may contain from one to 18 carbon atoms, it preferably contains one to four carbon atoms. Illustrative alcohols include methanol, ethanol, propanol, butanol, pentanol, hexanol, etc.

Another reactant used in preparing the mixture of the present invention is an amino compound. An amino compound is used to prepare each of the components of the mixture and the amino compound used in each of the steps may be of the same chemical composition or of different chemical composition but will be selected from the following.

1. Monoamine containing from about eight to about 26 carbon atoms and is referred to herein as a long-chain alkyl monoamine. The monoamine may be a primary, secondary or tertiary-alkyl amine and preferably is a primary or secondaryalkyl amine. Preferred monoamines include octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, eicosylamine, heneicosylamine, docosylamine, tricosylamine, tetracosylamine, pentacosylamine and hexacosylamine. The amines conveniently are prepared from fatty acid derivatives and may comprise, oleyl example, tallow linoleyl hydrogenated tallow amine, lauryl amine, stearyl amine, oleyl amine, limoleyl amine, soya amine, coconut amine, etc. Also included are the beta-alkyl amines, also referred to as beta-amine, in which the nitrogen atom is attached to the beta or second carbon atom of the alkyl group.

2. N-alkyldiaminoalkanes containing from about eight to about 26 carbon atoms in said alkyl and from about two to about six carbon atoms in said alkane. Included particularly are the N-alkyl-l ,S-diaminopropanes in which the alkyl group contains from about eight to about 26 carbon atoms. These N- alkyl-l,3-diaminopropanes include N-octyl-l ,3- diaminopropane, N-nonyl-l,3-diaminopropane, N-decyl- 1 ,3- diaminopropane, N-undecyl-l,3-diaminopropane, N-dodecyl- 1,3-diaminopr0pane, N-tridecyl-l,3-diaminopropane, N- tetradecyll ,S-diaminopropane, N-pentadecyl- 1 ,3- diaminopropane, N-hexadecyl-l,3-diaminopropane, N-heptadecyl-l,3-diaminopropane, N-octadecyl-l,3- diaminopropane, N-nonadecyl-l,B-diaminopropane, N- eicosyll ,3-diaminopropane, N-heneicosyll ,3- diaminopropane, N-docosyl-l,3-diaminopropane, N-tricosyl- 1,3-diaminopropane, N-tetracosyl-1,3-diaminopropane, N- pentacosyll ,3-diaminopropane and N-hexacosyl- 1,3diaminopropane. Included particularly are the N-alkyl-l,3- diaminopropanes in which the alkyl group is derived from tallow and are available commercially as Duomeen T and Diam 26. These commercial diamines comprise a mixture in which the alkyls predominate in 16 to 18 carbon atom groups. Also included are the correspondingly substituted diaminoethanes, diaminopropanes, diaminobutanes, diaminopentanes and diaminohexanes.

Other diaminoalkanes are the beta-alkyldiamines, in which at one alkyl group is attached to a nitrogen atom at the beta or second carbon atom of the alkyl group. Such an amine is available commercially under the trade name of Duomeen L-l5 and is a N-beta-alkyl-propylenediamine in which the alkyl group contains 17 carbon atoms. This compound also may be named N-l-methyl-heptadecylpropylenediamine. It is understood that other beta-alkyldiamines may be employed and will comprise N-l-methyl-alkyl-alkylenediamine in which the alkyl moiety, exclusive of the methyl group, contains from about seven to about 25 carbon atoms which means that the total number of carbon atoms in the alkyl group contains from about eight to about 26 carbon atoms.

As hereinbefore set forth, the mixture of the present invention includes a salt of a phosphorus compound and an amino compound. The phosphorus compound for use in preparing the salt is prepared by the oxyalkylenation of an alcohol, which may be of aliphatic or aromatic configuration, and then forming the phosphate thereof. Aliphatic alcohols for oxyalkylenation may be saturated or unsaturated and preferably contain at least four carbon atoms and more particularly from about six to 20 or more carbon atoms. Illustrative alcohols include butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecyl alcohol, eicosyl alcohol, etc. These alcohols conveniently are derived from fatty acids and accordingly include, for example, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, decylenyl alcohol, dodecylenyl alcohol, palmitoleyl alcohol, oleyl alcohol, linoleyl linolenyl alcohol, gadoleyl alcohol, etc.

Aromatic alcohols include phenol and particularly alkyl phenols. The alkylphenols preferably contain at least four and more particularly from about six to about 20 carbon atoms in the alkyl group. Illustrative alkylphenols include hexylphenol, heptylphenol, octylphenol, nonylphenol, decylphenol, undecylphenol, dodecylphenol, tridecylphenol, tetradecylphenol, pentadecylphenol, hexadecylphenol, heptadecylphenol, octadecylphenol, nonadecylphenol, eicosylphenol, etc., as well as dialkyl and trialkylphenols in which the alkyl groups are selected from those hereinbefore specifically set forth. Also, the polyalkylphenols may contain one or more alkyl groups containing from one to six carbon atoms and one or more alkyl groups containing from six to 20 carbon atoms.

Oxyalkylenation of the aliphatic or aromatic alcohol is effected in any suitable manner. While ethylene oxide is preferred for reaction with the aliphatic or aromatic alcohol, it is understood that propylene oxide, butylene oxide, pentylene oxide, hexylene oxide, etc., may be used. The Oxyalkylenation is effected by reacting the aliphatic or aromatic alcohol with the alkylene oxide, particularly ethylene oxide, in the molar ratios to produce the oxyalkylenated alcohol or phenol containing the oxyalkylenated group in the desired proportion. In a preferred embodiment, the oxyalkylenated alcohol or phenol contains from two to about 12 or more and particularly from two to about six oxylakylene groups. The oxyalkylenation is effected in any suitable manner and generally will be conducted at a temperature of from ambient to about 175 C. and more particularly from about 90 to about 150 C., preferably in the presence of a catalyst such as sodium hydroxide, potassium hydroxide, tertiary amine, quaternary hydroxide, etc. When the oxyalkylenation is to be limited to the addition of one oxy group, the catalyst is used with the alkanols but may be omitted with the alkylphenols. superatmospheric pressure may be employed and may be within the range of from about 10 to 1000 pounds or more.

The oxyalkylenated aliphatic or aromatic alcohol then is reacted in any suitable manner with P to form the desired phosphate. One molar proportion of P 0 or other suitable phosphorus oxide is reacted per one or two molar proportions of the oxyalkylenated hydrocarbon. In general, an excess of P 0 is employed in order to insure complete reaction. The reaction is effected at a temperature within the range of from ambient to about 110 C. and under substantially anhydrous conditions. The resultant free acid form of the phosphate generally is recovered as a viscous liquid.

As hereinbefore set forth, one component of the mixture of the present invention is the reaction product of the polycyclic acid or anhydride with the amino compound, both being selected from those hereinbefore set forth. The reaction product is prepared in any suitable manner and will depend upon whether the reaction product is to be a salt, prepared without the liberation of water, or an imide, amide, imideamide, amide-amide or ester, prepared with the liberation of water. When preparing the salt, mild conditions are employed to avoid the liberation of water. The salt may be either the mono or half salt or the double salt. When the mono or half salt is desired, the reactants are reacted in an equal mole proportion of acid and amine. When the double salt is desired the reactants are reacted in a proportion of 1 mole of acid and 2 moles of amine. As hereinbefore set forth, the salt is prepared under mild conditions and conveniently by intimately mixing the reactants at ambient temperature (about 10 to about 32 C.), although an elevated temperature which generally will not exceed from about 70 C. may be employed, particularly when the reaction is effected under superatmospheric pressure which may range from 5 to 500 p.s.i. or more. The time of mixing will be sufficient to effect substantially complete reaction and may vary from about 0.25 to 12 hours or more. A solvent preferably is used and conveniently comprises an aromatic hydrocarbon including benzene, toluene, xylene, ethylbenzene, cumene, or mixture thereof. Other solvents include paraffinic hydrocarbons, ethers, etc.

When the reaction is to be effected with the liberation of water, the reactants are reacted in a ratio of 1 mole proportion of the acid or derivative thereof and from 1 to 2 mole proportions of the amino compound. When an imide is to be formed, the anhydride preferably is used. When an amide is to be formed, the acid preferably is used. When an ester is to be formed, the acid or anhydride is used. The reaction with the liberation of water conveniently is prepared by first forming solutions in suitable solvent of one or both of the reactants, commingling the reactants and heating the mixture under refluxing conditions. The refluxing temperature generally will range from about to about 280 C. and the pressure will range from about 5 to 500 p.s.i. or more, with the time of refluxing being within the range of from about 0.5 to 12 hours or more. The water formed during the reaction preferably is continuously removed from the reaction zone. When the N-alkyldiaminoalkane and the anhydride are used as reactants and the reaction mixture is refluxed as above described, it is believed that the reaction product is an imide-amine.

The reaction product formed in the above manner comprises one component of the novel composition of the present invention. The second component of the mixture is the salt of a phosphorus compound and an amino compound. As hereinbefore set forth, the amino compound will be selected from those hereinbefore specifically set forth, as also will be the phosphorous compound. The salt is prepared in any suitable manner and conveniently by mixing the amino compound and the phosphorus compound at ambient temperature or an elevated temperature which generally will not exceed about 70 C. The mixing may be effected at atmospheric pressure or, when desired, superatmospheric pressure in the range of from about 5 to about p.s.i.g. or more. The time of mixing will range from a fraction of an hour to 24 hours or more and generally from about one-fourth to about 4 hours. When desired, the phosphor-containing compound may be prepared as a solution in a suitable solvent and then commingled with the amino compound. Conveniently the solvent will be the same as used in the other step of the process.

In general, the neutral salt of the phosphorus compound and amino compound is preferred. The neutral salt is preferred by using stoichiometric equivalents of the amino groups and of the acid groups. Thus, the specific concentrations of reactants will depend upon whether the orthophosphate salt or pyrophosphate salt is to be prepared and whether a monoamino compound or a polyamino compound is used. The basic salt is prepared by utilizing a deficiency of acidic equivalents and similarly the acid salt is prepared by using a deficiency of basic equivalents. The proportions of reactants used in preparing the salt may range from about 0.1 to 1 basic equivalent per one acidic equivalent or from about 0.1 to l acidic equivalent per 1 basic equivalent and preferably from 0.25 to 1 equivalent of one component per 1 equivalent of the other component.

The reaction product and the salt may be each recovered in the presence of a solvent and used in this manner to form the mixture of the present invention or, when desired, the solvent may be removed from one or both of the components in any suitable manner. When the product is recovered in the absence of a solvent, a solvent may be incorporated in the mixture to improve solubility of the mixture in the substrate. Particularly suitable solvents for this purpose include alkylphenols and polyalkylphenols in which the alkyl group or groups contain from six to 20 carbon atoms each. The phenol may be used in a concentration of 5 percent and preferably from 20 percent to 200 percent by weight of the active components of the mixture.

The reaction product and the salt will be used in any suitable proportions. While these may be expressed as mole proportions, advantages appear to express these proportions as the ratio of halogen and particularly chlorine to phosphorus in the final mixture. It will be noted that the specific acids hereinbefore set forth contain six chlorines per molecule. When expressed in this manner, the reaction product and salt may be used in a halogen and particularly chlorine to phosphorus ratio of from 0.1 to about 300 and preferably of from about 12 to about 100.

As hereinbefore set forth, the mixture of the present invention is particularly advantageous for use in lubricating oil and particularly in lubricating oil which must meet severe requirements. It will be noted that the mixture of the present invention contains halogen, nitrogen and phosphorus in one embodiment and also sulfur in another embodiment. Experience has shown that compounds containing these elements are especially advantageous for use in lubricating oils subject to severe conditions. However, while the reaction mixture of the present invention is especially useful in such lubricating oils, it is understood that it also is used to advantage in other lubricating oils. Another advantage of the compositions of the present invention is that certain of these compositions'will not cause darkening of the oil during use.

The lubricating oil may be of natural or synthetic origin. The mineral oils include those of petroleum origin and are referred to as motor lubricating oil, railroad-type lubricating oil, marine oil, transformer oil, turbine oil, differential oil, diesel lubricating oil, gear oil, cylinder oil, specialty products oil, etc. Other natural oils include those of animal, marine or vegetable origin.

Synthetic lubricating oils are of varied types including aliphatic esters, polyalkylene oxides, silicones, esters of phosphoric and silicic acids, highly fluorine'substituted hydrocarbons, etc. Of the aliphatic esters, di-(2-ethylhexyl) sebacate is being used on a comparatively large commercial scale. Other aliphatic esters include dialkyl azelates, dialkyl suberates, dialkyl pimelates, dialkyl adipates, dialkyl glutarates, etc. Specific examples of these esters include dihexyl azelate, di-( Z-ethylhexyl) azelate, di-3,5,5-trimethylhexyl glutarate, di-3,5,5-trimethylpentyl glutarate, di-(Z-ethylhexyl) pimelate, di-( 2-ethylhexyl) adipate, triamyl tricarballylate, pentaerythritol tetracaproate, dipropylene glycol dipelargonate, l,5-pentane-diol-di-( 2-ethylhexanonate), etc. The polyalkylene oxides include polyisopropylene oxide, polyisopropylene oxide diether, polyisopropylene oxide diester, etc. The silicones include methyl silicone, methylphenyl silicone, etc., and the silicates include, for example, tetraisooctyl silicate, etc. The highly fluorinated hydrocarbons include fluorinated oil, perfluorohydrocarbons, etc.

Additional synthetic lubricating oils include (1) neopentyl glycol esters in which the ester group contains from three to 12 carbon atoms or more, and particularly neopentyl glycol propionates, neopentyl glycol butyrates, neopentyl glycol caproates, neopentyl glycol caprylates, neopentyl glycol pelargonates, etc., (2) trimethylol alkanes such as trimethylol ethane, trimethylol propane, trimethylol butane, trimethylol pentane, trimethylol hexane, trimethylol heptane, trimethylol octane, trimethylol decane, trimethylol undecane, trimethylol dodecane, etc., as well as the esters thereof and particularly triesters in which the ester portions each contain from three to 12 carbon atoms and may be selected from those hereinbefore specifically set forth in connection with the discussion of the neopentyl glycol esters, and (3) tricresylphosphate, trioctylphosphate, trinonylphosphate, tridecylphosphate, as well as mixed aryl and alkyl phosphates, etc.

The present invention also is used in the stabilization of greases made by composting one or more thickening agents with an oil of natural or synthetic origin. Metal base synthetic greases are further classified as lithium grease, sodium grease, calcium grease, barium grease, strontium grease, aluminum grease, etc. These greases are solid or semisolid gels and, in general, are prepared by the addition to the lubricating oil of hydrocarbon-soluble metal soaps or salts of higher fatty acids as, for example, lithium stearate, calcium stearate, aluminum naphthenate, etc. The grease may contain one or more thickening agents such as silica, carbon black, talc, organic modified Bentonite, etc., polyacrylates, amides, polyamides, aryl ureas, methyl N-n-octadecyl terephthalomate, etc. Another type of grease is prepared from oxidized petroleum wax, to which the saponifiable base is combined with the proper amount of the desired saponifying agent, and the resultant mixture is processed to produce a grease. Other types of greases in which the features of the present invention are usable include petroleum greases, whale grease, wool grease, etc., and those made from inedible fats, tallow, butchers waste, etc.

Oils of lubricating viscosity also are used as transmission fluids, hydraulic fluids, industrial fluids, etc., and the novel features of the present invention are used to further improve the properties of these oils. During such use the lubricating oil which is used for this purpose is improved by incorporating the additive of the present invention.

Oils of lubricating viscosity also are used as cutting oils, rolling oils, soluble oils, drawing compounds, etc. In this application, the oil is used as such or as an emulsion with water. Here again, it is desired that the oil serves to lubricate the metal parts of saws, knives, blades, rollers, etc., in addition to dissipating the heat created by the contact of the moving metal parts.

Oils of lubricating viscosity also are used as slushing oils. The slushing oils are employed to protect finished or unfinished metal articles during storage or transportation from one area to another. The metal articles may be of any shape or form including steel sheets, plates, panels, coils, bars, etc., which may comprise machine parts engines, drums, piston rings, light arms, etc., as well as farm machinery, marine equipment, parts for military or other vehicles, household equipment, factory equipment, etc. A coating which may be visible to the eye, or not, as desired, covers the metal part and protects it from corrosion, etc.

While the mixture of the present invention is particularly advantageous in substrates subjected to high temperatures, it is understood that it may be used in other substrates which deteriorate in storage, during treatment and/or use. These other substrates include motor fuels such as unsaturated gasoline, blends of unsaturated and saturated gasolines, etc., jet fuel, diesel oil, fuel oil, residual oil, drying oil, rubber, polyolefins, resins, waxes, etc.

The mixture of the present invention is used as an additive in lubricating oil in a small but stabilizing concentration. Depending upon the particular use, the additive may be employed in a concentration of from about 0.01 percent to about 25 percent and preferably from about 0.05 percent to about 10 percent by weight of the oil. These and the following concentrations are on the basis of the active constituent and do not include the solvent or solubilizing phenol when used. When used in conventional lubricating oil, the additive generally is employed in a concentration of from about 0.01 percent to about 2 percent by weight of the oil. When used in lubricating oil for more severe operations, such as hypoid gear oil, the additive is used in a concentration of from about 1 percent to about 20 percent or more by weight of the oil. In general, substantially the same range of additive concentration is employed when the oil is used as transmission fluid, hydraulic fluid, industrial fluid, etc. When the oil is used in the formulation of a grease, the additive is used in a concentration of from about 0.5 percent to about percent by weight of the oil. When used in cutting oil, rolling oil, soluble oil, drawing compound, etc., the additive may be used in a concentration of from about 0.1 percent to about percent by weight of the oil. When used in slushing oil, the additive may be used in a concentration of from about 0.1 percent to about percent by weight or more of the oil.

It is understood that the mixture of the present invention may be used along with other additives incorporated in the oil for specific purposes. In most cases, it is desirable to also incorporate an additional antioxidant in the oil. Preferred additional antioxidants are of the phenolic type and include tertiarybutylcatechol, 2,6-ditertiarybutyl-4-methylphenol, 2,4- dimethyl-6-tertiarybutylphenol, etc., 2-tertiarybutyl-4- methoxyphenol, 2-tertiarybutyl-4-ethoxyphenol, etc. Also, other additives incorporated in lubricating oil include metal deactivator, dye, viscosity index improver, pour point depressor, antiforming additive, detergent, etc. In some cases, particularly when used with the additional antioxidants set forth above, a synergistic effect is obtained and thus an even greater improvement in the properties of the substrate is obtained.

While the mixture of the present invention is particularly useful in lubricating compositions, it also possesses insecticidal properties and may be used for this purpose. Furthermore, the mixtures also possess flame proofing or flame-retardant properties and therefore are useful in plastic coatings, paints, drying oils, etc., as well as in fibrous materials. For example, in textiles, the mixture imparts flame-retardant as well as fungicidal properties to the fabric.

The following examples are introduced to illustrate further the novelty and utility of the present invention but not with the intention of unduly limiting the same.

EXAMPLE I The reaction product was prepared by first adding about 4,000 g. of toluene to a reactor and then slowly adding thereto, with stirring, 1,700 g. (4 mole) of 5,6,7,8,9,9-hexachloro-1,2,3 ,4,4a,5 ,8,8a-octahydro-5,8-methano-2,3- naphthylenedicarboxylic anhydride, after which 1,070 g. (4 mole) of oleylamine were added with stirring. The mixture then was subjected to refluxing and a total of 79 cc. of water was collected. The reaction mixture was allowed to cool and then treated with potassium carbonate. The resultant imide was recovered as a viscous amber oil and was analyzed and found to have a bromine number of 23.5, which corresponds to the theoretical bromine number of 23.8, a total nitrogen content of 1.97 percent which corresponds to the theoretical of 2.08 percent, a total chlorine content of 32.1 percent which corresponds to the theoretical of 31.75 percent and a molecular weight of 630 which corresponds to the theoretical of 671.

The mixture of this example was prepared by commingling the reaction product prepared in the above manner with a phosphate salt prepared by the reaction of oleylamine with polyoxyethylenated nonylphenol phosphate containing an average of about 5 oxyethylene groups. The oxyethylenated nonylphenol phosphate is a liquid at room temperature and has a phosphorus content of 4.9 percent and a specific gravity at 25 C. of 1.07. The salt was prepared by mixing at room temperature 108 g. (0.4 equivalents) of oleylamine and 236 g. (0.4 equivalents) of the polyoxyethylenated nonylphenol phosphate, then warming on a steam bath and further mixing. The salt was recovered as a clear, amber, viscous liquid.

The reaction product and the salt, prepared as described above, were commingled to form a mixture having a chlorine:phosphorus ratio of 24: 1. This mixture as used in different concentrations as an additive in lubricating oil as will be illustrated in a subsequent example appended to the present specifications.

EXAMPLE II The mixture of this example includes, as one component, the reaction product prepared as described in example I and, as the other component, a salt prepared from polyoxyethylenated nonylphenol phosphate having an average of 1.5 oxyethylene groups and N-tallow-l,3-diaminopropane. The oxyethylenated nonylphenol phosphate is a liquid at room temperature and has a phosphorus content of 5.8 percent at 25 C. of 1.08. The N-tallow-l,3-diaminopropane is available commercially as Diam 26 and contains predominantly 16 to 18 carbon atoms in the tallow group. The salt is prepared by mixing at room temperature 51.7 g. (0.1 equivalents) of the polyoxyethylenated nonylphenol phosphate and 0.1 equivalents of the N-tallow-1,3-diaminopropane. After mixing at room temperature, the mixture is heated to form a homogeneous solution.

EXAMPLE III A mixture is prepared by first forming the reaction product using the anhydride described in example I with N alkyl-l,3- diaminopropane in which the alkyl contains 18 carbon atoms. This amine is available commercially under the trade name Duomeen L-15" and is a beta-alkyl diamine. The reaction product is prepared by refluxing at a temperature up to 120 C. 1700 g. (4 mole) ofA anhydride, 1,500 g. (4 moles plus 10 percent excess) of Duomeen L-15 and 3,000 g. of toluene. Approximately 92 ml. of water is removed during the refluxing which is continued until no more water is liberated. The reaction mixture is treated with anhydrous potassium carbonate and filtered. A g. sample of the reaction mixture is distilled to remove the solvent. The solvent-free product is a light amber oil having a basic nitrogen equivalent of 1.50 mg./g. which corresponds to the theoretical basic nitrogen equivalent of 1.515.

The salt used in this example is prepared by mixing at room temperature, 5 equivalent weights of stearyl amine and 5 equivalent weights of oxypropylenated tridecyl alcohol containing an average of two oxypropylene groups. The components are mixed at room temperature and warmed on a steam bath and further mixed.

The reaction product and salt then are commingled in proportions to form mixtures having chlorinezphosphorus ratios of6:l,12:1,18:1,24:1,30:l, 36:1,42:1,48:l and 54:1.

EXAMPLE IV The mixture of this example is prepared by first forming the reaction product of 1,4,5,6,7,7-hexachlorodicyclo-(2.2.1)-5- heptene-2,3-dicarboxylic anhydride and N-oleyl-l,3- diaminopropane. The other component of the mixture is a salt prepared by reacting N-oleyl-1,3-diaminopropane and polyoxyethylenated nonylphenol phosphate containing an average of 1.5 oxyethylenated groups. The reaction product and a salt are commingled to form a mixture having a mixture of chlorine:phosphorus ratio of 48: 1

EXAMPLE V The mixture of this example includes, as one component, the reaction product formed by reacting one mole proportion of 5 ,6,7 ,8 ,9,9-hexabromo-l ,2,3,4,4a,5 ,8,8a-octahydro- 1,4,5,8-dimethano-2,3-naphthalenedicarboxylic anhydride with one mole proportion of beta-diamine available commercially under the trade name of Duomeen L-15 and comprising N-l-methyl-heptadecyl-propylenediamine. The other component of the mixture is a salt prepared by reacting N-l methylheptadecyl-propylenediamine with oxyethylenated oc- 3,635,823 91 to tylphenol phosphate. The reaction product and the salt then of 6.82 percent by weight of the reaction product and 2.18 are commingled to form a mixture having a chlorinepercent by weight of the salt. phosphorus ratio of 36:1. Run No. 6 is a run made using the lubricating oil containing EXAMPLE VI a total additive concentration of percent by weight consist- 5 ing of 7.58 percent by weight of the reaction product and 2.42 As hereinbefore set forth the salt of the present invention is percent by weight of the salt.

TABLE 1 Temperature, F. Torque, lbs. Wear, teeth Total time at Temper- 50 pounds, ature,

250 500 750 1, 000 1, 250 250 500 750 1,000 250 250 500 750 1,000 1, 250 mins. F.

182 270 326 382 430 0-7 12-15. 17-18 21-22 21-25 0 0 2 2 18 45 430 NOTE. 5 Seizure. u A. u .2 of especial utility in substrates encountering high tempera- From the data in the above table, it will be seen that the diftures during use. An example of such a substrate is lubricating oil and especially such oil used in the lubrication of hypoid ferent concentrations of the mixture of the present invention all were effective in the evaluations for the full 45 minutes at gears which must meet severe requirements of high-torque 1,250 pounds. Of importance also is the fact that there was no low-speed, low-torque high-speed and high-torque high-speed conditions. The requirements are even more severe because such oils must retain their lubricating properties for long periods of time as exemplified, for example, by the recommendations of not changing oil for one year or more or 20,000 25 miles or more of operation and even up to 100,000 miles or for the life of the vehicle.

One method of evaluating E.P. (extreme pressure) lubricat- I ing oils is by the F alex machine. This procedure is described in darkening of the oil after the evaluations, thus further demonstrating the high thermal and hydrolytic stability of the mixture.

EXAMPLE VII Another advantage of the mixture of the present invention is that it is of high thermal and hydrolytic stability. This is demonstrated by the evaluations reported in the present example in which the mixture prepared as described in example I detail in a book entitled Lubricant Testing authored by E. and having the a chlorinezphosphoms ratio of 24:1 was evalu- G. Ellis and published by Scientific Publications (Great Britain) Limited, 1953, pages 150-154. Briefly, the Falex machine consists of a rotating pin which runs between two V"-shape bearings which are spring loaded against the pin and provided with means for varying the load. The oil to be tested is poured into a metal trough in which the pin and bearings are partly submerged. The machine was operated for 5 minutes each at 250, 500, 750, 1,000 pound loads and for minutes at 1,250 pound load. The data collected includes the temperature of the oil at each of the loads and the torque in pounds per square inch at each load, as well as the wear which is determined at a ratchet wheel arrangement in which the teeth are advanced in order to maintain the desired load. Each tooth is equivalent to approximately 0.000022 inches. 45

Preferred additives are those which impart low temperature, low torque and low wear to the oil. The lubricating oil used in this example is a commercial lubricating oil having a S.A.E. rating of which was obtained free of additives.

In another method the machine was operated for 5 minutes 5 means that the oil is operating satisfactorily at a higher temperature. In this series of evaluations the mixtures used has a chlorine: phosphorus ratio of 24:1 but the variable of this example is that different concentrations of the mixture were evaluated.

Run No. l in the following table is a run made using the 60 lubricating oil not containing an additive and thus is the blank or control run.

Run No. 2 is a run made with the lubricating oil containing 6 percent by weight of total additive consisting of 4.55 percent by weight of the reaction product and 1.45 percent by weight of the salt.

Run No. 3 is a run made with the lubricating oil containing a total of 7 percent by weight of the additive consisting of 5.31 percent by weight of the reaction product and 1.69 percent by weight ofthe salt.

Run No. 4 is a run made with the lubricating oil containing a total additive concentration of 8 percent by weight consisting of 6.06 percent by weight of the reaction product and 1.94 percent by weight of the salt.

Run No. 5 is a run made using lubricating oil containing a total additive concentration of 9 percent by weight consisting ated in a commercial gear oil to determine the coefficient of boundary friction. This evaluation was made in a modified Bowden-Leben pin and disc machine. The Bowden-Leben method is described in The Friction and Lubrication of Solids, 1954, page 74, by Bowden and Tabor. This method is also discussed in the article by E. Rabinowicz, entitled The Boundary Friction of Very Well Lubricated Surfaces, which was presented at the A.S.L.E. Ninth Annual Meeting in Cincinnati on Apr. 5, 1954, and published in the July-Aug. 1954 40 issue of Lubricating Engineering. In the modification used for the run reported herein, a highly polished steel disc rotates in contact with an upwardly rounded steel pin. The pin and disc then are immersed in a pan containing the oil to be evaluated. The equipment is enclosed in a housing which is heated for varying the temperature of the run which, in this experiment, ranged from to 350 F. The equipment also includes a variable speed reducer for varying the rpm. of the disc and also means for varying the load. 1n each run the wear or break-in period consists of gradually increasing the speed to 12 r.p.m. at 2,000 g. load and decreasing the speed to 12 rpm, after which the speed is increased to 196 rpm. The load varied from 500 g. to 2,000 g. and the coefficient of friction was determined at r.p.m.s decreasing from 196 to 0.1. A strain gage circuit is used as sensing element in converting the frictional effects into equivalent electrical responses which then are recorded on a continuous chart recorder.

Run No. 7 in the following table is a run made with the gear oil containing 10 percent by weight of the mixture prepared as described in example I having a chlorine:phosphorus ratio of 24:1.

TABLE 11 Run 7 100 F. 200 F. 275 F. 350 F.

0. 072 0. 084 0. 086 0. 085 0. 075 0. 085 0. 088 0. 085 0.077 0. 088 0. 090 0. 085 0. 079 0. 090 0. 090 0.085 0. 082 0.092 0. 090 0, 084 0. 085 0. 093 0. 093 0.080 0. 087 0. 097 0. 005 0. 07.) 0. 090 0. 097 0. 097 0.075 0. 003 0. 098 0. 095 0. 074 0. 0. 100 0. 098 0. 067 0. 105 0. 100 0. 196 0. 043 0. 106 0. 099 0. 092 0. 027 0. 103 0. 100 O. 086 0. 022 0. 100 O. 097 O. 072 0. 012 0. 002 0.0514 0v 056 0. 00s 0. 005 0. 005

From the data in the above table, it will be seen that the mixture of the present invention has high stability and imparts low coefficient of friction to the oil. These properties indicate that the additive would be effective for limited slip differential Referring to data in the above table, it will be seen that the mixture of components resulted in a seizure of 2,100 pounds whereas the use of each of the components separately had seizure loads of 1,000 and 1,500 pounds, respectively. This application. again demonstrates the synergistic effect obtained through the use of the mixture as compared to the use of each component EXAMPLE VIII Separately In order to determine whether the addition of water would EXAMPLE X be harmful, another evaluation was made in the same manner as described in example VII except that 1 percent by weight of The mixture prepared as described in example I is used in a water was added to the used oil after evaluation as described concentration of 1 percent by weight as an additive in grease. in example VII and additional evaluation then was made on The additive is incorporated in a commercial Mid-Continent the used oil. These results are reported in the following table. lubricating oil having an S.A.E. viscosity of 20. Approximately The run reported in the following table was made with the l 5 92 percent of the lubricating oil then is mixed with approxioil containing the mixture prepared as described in example I mately 8 percent by weight of lithium stearate. The mixture is and corresponds to the run reported in example VII. heated to about 450 F with constant agitation. Subsequently TABLE In the grease is cooled, while agitating, to approximately 250 F.

Run 8 and then the grease is further cooled slowly to room temperature. 100 F. 200 F. 275 F. 35 F. The stability of the grease is tested in accordance with Speed. ASTM D942 method, in which method a sample of the grease H 8.82 8-822 8-8 8-825 is placed in a bomb and maintained at a temperature of 250 1 5 0:074 050 F. Oxygen is charged to the bomb, and the time required for a 8-8;? 3-323 8-82? 8-81? drop of 5 pounds pressure is taken as the Induction Period. A 080 084 0:063 0:044 sample of the grease without additive will reach the Induction 0-082 0-087 [1060 1 Period in about 8 hours. On the other hand, a sample of the 8881 8188 8:888 818%; grease containing 1 percent by weight of the additive will not 085 097 052 030 reach the Induction Period for more than 100 hours. 8: 88,1 8:888 88:8 8: 888 We claim as our invention: 8822 8-8;? 8-813 8-888 1. Synergistic mixture of (l) the product formed by the 9:092 0:101 0:045 0:012 reaction, at a temperature of about 10 to about 280 C., of 0-093 0-100 0-035 0012 from one to two mole proportions of amino compound and one mole proportion of polyhalopolyhydropolycyclicdicar- It will be seen that the mixture of the present invention was boxylic i or anhydride and 2 Salt f oxyamylenated effective in the Presence of water and therefore is g y cohol phosphate and amino compound, the amino compounds desirable in case water should become entrained in the f 1 d 2 being independently Selected f the group lubricating consisting of long-chain alkyl monoamine and N-alkyldiaminoalkane containing from about eight to about 26 car- EXAMPLE IX bon atoms in said alkyl and from about two to about six car- As hereinbefore set forth, a synergistic effect was obtained atoms in Said alkanewhen using a mixture of the components as compared to the The mixture of claim 1 wherein said acid y is use of each component separately. This is demonstrated by i i y -i the data in the present example which compares the use of l) methano'z,3naphthylenedicarboxyfic acid anhydridethe reaction product as described in example I and (2) the The mixture of Claim 1 wherein said long-chain alkyl phosphate salt prepared by the reaction of oleyl amine with monoamine contains from about eight to about 26 carbon polyoxyethylenated nonylphenol containing an average of atomsabout 5 oxyethylenated groups. The mixture of ti 4. The mixture of claim 3 wherein said monoamine IS a fatty product and salt was prepared to have a chlorine:phosphorus acid amineratio of 24:1. 5. The mixture of claim 4 wherein said fatty acid amine is Run No. 9 in the following table is a run using 10 percent by oleyl aminei h f h reaction d 6. The mixture of claim 4 wherein the fatty acid amine is Run No. 10 in the table is a run made using 10 percent by t yl i i h of h phosphate l 7. The mixture of claim 1 wherein said N-alkyl-diaminoal- Run No. 11 in the table is a run made using a mixture of k i l y -L i min Pr P n 6.82 percent by weight of the reaction product and 2.18 per- The miXtule of claim 1 wherein Said Phosphate is 3 cent by weight of the phosphate salt. It will be noted that the kylenated alkylphenoi phosphate containing one to 12 oxyaimixture is used in a total additive concentration of 9 percent kylene groups of from two to six carbon atoms each and havb i h ing from four to 20 carbon atoms in the alkyl group.

TABLE IV Composition, wt. percent R e;c Temperature, F. Torque, in. lbs. Run tion Phosphate No. product salt 250 500 750 1,000 1,250 1,500 1,750 2,000 250 500 750 1,000 1,250 1,500 1,750 2,000 0 V 10, 0 209 250 350 540 7-0 12-15 16-28 36-60 10 10.0 250 323 373 407 438-8 0-7 12-14 18-19 22-23 25-20 28 l00 11. 6. 82 2.18 272 341 300 425 452 477 521 0-7 13-15 18-19 21-23 23-26 25-29 2629 30-32 Wear, teeth MFST seizure conditions Load, Time, Tempera- Ruii No 250 500 750 1,000 1,250 1,600 1,750 2,000 pounds minutes ture, F. 0 2 2 28 1, 000 5 540 0 1 2 8 2 0-s 1,500 1.0 438 0 0 3 1 5 3 6 23 2,100 0 567 9. An organic substrate normally subject to deterioration in storage or use containing a stabilizing concentration of the additive of claim 1.

10. The organic substrate of claim 9 being a lubricant comprising a major proportion of an oil of lubricating viscosity.

11. The organic substrate of claim 10 being lubricating oil. 

2. The mixture of claim 1 wherein said acid or anhydride is 5,6, 7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3 -naphthylenedicarboxylic acid or anhydride.
 3. The mixture of claim 1 wherein said long-chain alkyl monoamine contains from about eight to about 26 carbon atoms.
 4. The mixture of claim 3 wherein said monoamine is a fatty acid amine.
 5. The mixture of claim 4 wherein said fatty acid amine is oleyl amine.
 6. The mixture of claim 4 wherein the fatty acid amine is stearyl amine.
 7. The mixture of claim 1 wherein said N-alkyl-diaminoalkane is N-alkyl-1,3-diaminopropane.
 8. The mixture of claim 1 wherein said phosphate is oxyalkylenated alkylphenol phosphate containing one to 12 oxyalkylene groups of from two to six carbon atoms each and having from four to 20 carbon atoms in the alkyl group.
 9. An organic substrate normally subject to deterioration in storage or use containing a stabilizing concentration of the additive of claim
 1. 10. The organic substrate of claim 9 being a lubricant comprising a major proportion of an oil of lubricating viscosity.
 11. The organic substrate of claim 10 being lubricating oil. 